Herbicidal nematocidal and fungicidal method



United States Patent 3,175,896 Patented Mar. 30, 1965 3,175,896 EERBICIDAL NEMATOCIDAL AND FUNGICIDAL METHOD Friedrich Arndt, Bcrlin-Frohnau, Alfred Czyzewski, Berlin-Tempelhof, Eugen Griehsch, Berlin-Britz, and Gerhard Liedtke, Berlin-Reinickendorf, Germany, assignors to Schering, A.G., Berlin, Germany No Drawing. Filed Nov. '7, 1961, Ser. No. 150,634 Claims priority, application Germany, Nov. 15, 1960, Sch 28,776 7 Claims. (CI. 71-25) This invention relates to chemical pest control agents, and more particularly to chemical agents which have 4 selective biocidal effects on certain weeds, on fungi, and on nematodes, and to methods of protecting vegetal crops by the use of such agents.

The pest control agents of the invention are carbodiimide compounds of the formula wherein R and R represent organic radicals of the group consisting of lower alkyl; cycloalkyl having a saturated carbon ring of 5 to 8 members, one of the members being directly connected to one of the nitrogen atoms of the formula; lower allaenyl; radicals of the formula --Alk--X wherein All; is lower alkylene and X is lower alkoxy, phenyl, lauroxy, or morpholyl; radicals of the formula Lead oxide may be substituted for mercury oxide in the reaction of Formula 2. The tln'ourea derivatives are also converted to the corresponding carbodiimide derivatives by oxidation with alkaline hypochlorite solutions.

Most of the compounds or Formula 1 are capable of being distilled at reduced temperature, and Table 1 lists boiling points of representative examples of carbodimides suitable for the plant protection method of the invention together with the pressure at which the boiling point is measured. The radicals R and R are listed, and will be understood to be linked by the group --N=C=N--.

Table I Boiling Point mm. Hg

Oyelopentyl Cyclopentyl Cyclohexyh Cyclohexyl coca dscncboo Boiling Point.

R1 R2 7 mm. Hg. C.

Propyl Phenyl 0.9 81-82 Isopropyl dn 0. 2 60-61 Sec.-Buty1 do 0. 5 78-80 HBXYL 13 160-163 Isopropyl 4-fluorophenyl .0. 2 Allyl. dn 1. 5 92-97 Isopropyl -3-chlorophenyl 0. 5 -87 Do 4-bromophenyL- 1. 0 109-113 3nitrophenyl 0.5 123-125 -2-methylphenyl 2 85-86. 5 ZethoxyphenyL. U. 8 -118 3-chloro-4-metl1y henyl 1. 5 119-121 a-Naphthyl 7 -137 13 40-43 15 56-61 0.6 144-145 1 68-70 0.6 112612? 3-meth0x r0 1. 1 Benz "K 12i 0, 4 75-77 B-Phenylcthyl 0. 6 94-97 Benzyl. .0. 5 132-134 B-Morpholinoethyh; 1.6 111-114 Isopropyl 5,6,7,8-tetrahydronaphthyl-l. 0, 8 135-139 The compounds defined herein can be incorporated with various materials to prepare the new compositions of the invention either in liquid or solid form.

For example, solutions of the compounds in organic solvents such as aromatic and aliphatic hydrocarbons, for instance benzene, xylene, cyclohexanol, ethylene chloride, methylene chlonide, can be applied directly as pesticides.

This method of application, however, is less favourable.

Suitable compositions are prepared by mixing the compounds with an inert solid carrier including magnesium and calcium carbonate, calcium sulphate, calcium phosphate, bentonite, kiesel-guhr, bleaching earth, and the like.

The percentage by weight of the essential active ingredient in these dust compositions will vary, but in gencral will be 0.5 to 95% by weight of the pesticidal composition.

Liquid pesticidal compositions consist for example of the compounds dissolved in an organic solvent or mixed with a solid carrier and homogeneously dispersed in water. To secure such homogeneous dispersion a surfaceactive agent may be used. These agents, especially of the anionic and nonionic type, cause the composition to be easily dispersed in water to give aqueous sprays which constitute a most desirable form of application.

Generally the surface-active agent will not comprise more than 30% by weight of the composition. Usually the minimum will be 0.1%.

The solvents used include benzene, xylene, kerosene, methyleneohloride, chloroform, and the like. In the same way the compounds also may be incorporated in oils, such as parafiin oil; and the like.

The inert solid carriers include those mentioned above;

In another method for application especially for weed control the compounds may be combined with other herbicides such as isopropyl-N-phenyl-carbamate, 'isopropyl- N-(3-ch1or'ophenyl) carbamate, 2-chloro 4 isoprop-ylamino-6-ethylamino-1,3,5-triazin, the alkali salts of 4- chloro-Z-methyl-phenoxyacetic acid or other known herbicides.

They also may be mixed with solid fertilizers to iorrn either powdery or granular compositions that can be used in the cultivation of agricultural crops.

Typical examples or preparing the new compositions are as follows:

(1) 20 p-ts. :of a 'carbodiimide are dissolved in 60 pts. of xylene and mixed with 20 pts. of a tributylphenol-polyglycol-ether (i.e. nonionic surface agent).

This composition is readily dispersible in water and provides an aqueous spray composition by mixing with WOO-10,000 pts. of water.

(2) 40 pts. of a carbodiimide are dissolved in 50 pts. of xylene and mixed with ms. of a mixture of the calcium salt of dodecylbenzene sulfonic acid, fatty acids polyglycolester, and tribut'ylphenolrpolyglycol-ether (i.e. anionic and nonionic surface agents).

This composition is well dispersible in water and gives stable emulsions.

This product provides a homogeneous powder suitable for application after'mixing with l00010,000 parts of water.

It is to be understood that this invention is not limited to these specific examples.

Several of the pest control agents of the invention may be employed jointly or simultaneously, and they may be combined with other pesticidal agents.

The agents also may contain additives such as binding agents, compressed gases, perfumes or stabilizers.

The pest control agents of the carbodiimide type have been found to be particularly useful for combatting weeds and other undesired vegetal growth. It is generally difli- .cult to combat weeds in vegetal crops selectively, particularly when the crop plants and the weeds are closely related, or belong to the same family of plants as is often the case. Known herbicidal agents which are suitable for application to the parts of plants which are exposed above ground, particularly the leaves, are limited in their utility to only one type or a few species of vegetal crops.

We'have now found that the N-substituted carbodiimide compounds are eifective in combatting weeds in the post-emergence stage without attecting many crop plants. Classes of plants which are protected to advantage by these pest control agents include plants of the family of Umbelliferae and Ammiaceae such as carrots, parsley, and dill, but also mangels and sugar beets, corn and other cereal crops. It is particularly noteworthy that certain substituted carbodiimide compounds are selectively tolerated by beets which are notoriously sensitive to herbicides applied to their leaves.

The field of application of the pest control agents of the invention is thus very wide. The herbicidal effects are greatest on the juvenile stages of the weeds affected. Pesticidal compositions of the invention suitable for weed control in crops are preferably applied in amounts 'between 1 and 4 kilograms per hectare (kg/ha.) based on the active ingredient. Such amounts are sufficient for the destruction of such important and common weeds as chickweed, groundsel, shepherds pouch, dead nettle, sowthistle, stinging nettle, goosefoot, and the like.

Considering the fact that so many vcgetal crops tolcrate the carbodiimide compounds without suffering sign1ficant damage, the broad spectrum of weeds affected 1s surprising.

Where the susceptibility of crop plants need not to be taken into consideration, the amount of pest control agents of the invention applied per unit area may of course be increased beyond the preferred range indicated above. Largeramounts are indicated where weeds are to be destroyed on walkways and i1 paved areas.

Carbodiimide compounds which have been found to be particularly effective when employed in the pest. control method of the invention include for instance:

d N,N'-dicyclopentyl) -carbodiimide N,N-di- (cyclohexyl) -carbodiin1id1e N,N'-di- (cycloheptyl -carbodiimide N,N'-dicyclooctyl) -ca rbodiimide N-allyl-N-cyclooctyl-carbodiimide N-isopropyl-N'-cyclooctyl-carbodiimide N-methyl-N-cyclooctyl-carbodiimide N-isopropyl-N-phenyl-carbodiimide The herbicidal effects and other specific advantageous fields of application of the pest control agents of the invention are illustrated by the following examples, but it will be understood that the invention is not limited to the specific embodiments chosen for the purpose of the disclosure.

EXAMPLE I Aqueous emulsions of the carbodiimide compounds listed in Table II below and containing the active ingredient in a concentration of 0.5 percent are sprayed on young test plants having a height of 10 to 20 centimeters. The tests are performed in a greenhouse under controlled conditions of temperature and moisture.

The plants employed are tomatoes and dwarf-beans. The active ingredients of the emulsions are identified by the radicals R and R in Formula 1. The effect on the treated plants is indicated by one of four code numbers which have the following meaning:

O---Destroyed 1Severly damaged 2--Damaged,

4-Slightly damaged Table II Effect on- Tomatoes Dwarf beans Cyclopentyl Cyclopentyl Cyclohexyl Cyelohexyl See-butyl. Hexyll lLlubWtLHOlQOHOpGnPNMLOMQOOQ womi-e-wwzommmoommoomwoomoooo Oleyl d0 Isopropyl 4-fluorophcnyl 1- 3 All 1 do 1 3-chlorophenyl. d-bromophenyl. 0- 1 D0 3-nitrophenyl 1- 1-2 Tert;.-b utyl t-chlorophenyl IsopropyL. .Z-methylphenyl Do 2-eth0xyphenyl Do 3-chloro-4-methylphenyl 1- Doa-Naphthyl 0 Do Isobutyl 3-4 Do Hexyl 0 y Oleyl 0 Isopropyl 4 o-Tolyl 0 2,4-dimethylphenyl- 2 4-chloro-2-methylphenyl 1 Furfuryl; 4 henyldo 0 IsopropyL. 3-methoxypropyl 2-3 2 Tert.-butyl 3-lauryloxypropyl 0 IsopropyL. 0

D 0 Benzyl y 0 'lert.-butyl ,d-ltrorpholinoethyl 3-4 Isopropyl 5,G,7,8-tetrahydro- 1 0- naphthyl-l;

vmooicmimotowcocconowp .5 EXAMPLE 2 N,N di(cyclohexyl) carbodiimide, N,N' di(cyclooctyl)-carbodiimide, and N-tert-b'utyl-N-(S-Iauryloxypnopyl)-carbodiimide are emulsified in water to a concenparsley are in a somewhat more mature stage than those treated in Example 2. They react in a similar manner as in Example 2. The results achieved are tabulated on Table IV using the same scale of evaluation as in Table III.

sprayed on respective carrot fields in such amounts as to deposit 2 kg./ha. of the two first-mentioned carbodiimide compounds and 1 kg./ha. of the last mentioned compound. The carrots are in the germination to twoleaf stage and show no adverse effects from the treatment. Accompanying weeds originating from contaminated carrot seeds are destroyed or severely damaged as seen from Table III in which the eifects of the treatment are evaluated on an arbitrary scale ranging from 10 (no noticeable eiiect) to (fully destroyed). The carbodiimide U compounds are identified by the substituent radicals R and R in Formula 1.

Table -l V R1 R1; Active Parsley Galinsoga Senecio Agent parviflora vulgaris Cyclohexyl Oyclohexyl 2 10 6 Cyclooctyl..- .Cyclooetyl .n 2 10 3 5 1 tert.-Butyl 3-lauryloxypropyL 2 5 Chenopodium Um'ca Panicum um mans aanguz'nale CyelohexyL- 1 1 Oyclooctyl- 0 5 0 10 tert.-Butyl 0 10 tration of 1 kg. per 1000 liters. The emulsions are p EXAMPLE 4 Portions of a sugar beet field infested with Weeds in a aged by the pest control agents, but selective resistance.

to some of them by some Weeds indicate the need for combined application of several carbodiimide compounds.

Table III Active Lamium Senecto R R1 Agent Carrots amplextuulgam caule CyclohexyL 2 10 1.8 0.3 Cyclooctyl. 2 10 1 1 tart-ButyL. 3-lauryloxyp 1 10 0 Chenopodium Galinsoga Capsella buralbum parvz'flom 8a pusloris Cyclohexyl. 0.3 0.5 0 Cyclooctyl. 0. 3 0 0 tert.-Buty1. 0.5 1.5

Thlaspi Stellana Urtz'ca Panicum arvense media wens sctaria Cyclohexyl Cyclohexyl 0 1 Cyclooetyl CyelooctyL 0 1 tert.-Butyl 3-lauryl0xypr0py 1 9 E 3 The results observed in the several sugar beet plots are tabulated in Table V in the same manner as in the preceding examples.

Table V R R Active Sugar Galinsoga Senecio Sonchus Agent Beets parvtjlom vulgaris oleraceus Cyclohexyl Cyolohexyl 2 9 1 1 tert.-Butyl 3-lauryloxypropyl- 2 7 0 3 IsopropyL- henyl 4 i 7 0.5 1 llyl Cyclooctyl. 4 10 0. 5 1 Pheny urfuryl. 4 10 2 1 Gyclopent Cyclopentyl 1 l0 0 1 Oycloheptyl- Cyelohepty 0. 10 0.5 2 Cycloootyl GycloootyL..- 0.6 10 1 2 Methyl OyclohexyL- 2 8 0 1 Isopropyl Cyclooetyl 2 10 0 1 Table V-Cont1nued C'apsella Slallzzria Lamium Ohmopodi- Thlaspi R1 R1 bursa media amplezium album arvensc paaloris ccule Oyclohexyl Oyclohexyl O l tert.-B utyL- 3-lauryl0xypropyl. 4 4 2 Isopropyl. Phenyl 0 6 llyl. Oyclooctyl 0. 5 3 Phenyl- FurfuryL 2 9 3 Cyclopent Cyclopent 5 1 Cycloheptyl. Cy'cloheptyl. 6 2 Cyclooctylhu CyclooctyL- 5 2 Methyl Oyclohexyl 1O 1 Isopropyl Cyclooetyl 3 0 EXAMPLE 5 Emulsions are prepared from N,N-di-(cyclohexyl)- V such amounts as to deposit 5 and 7 kg. per ha. of the active compound.

The summer wheat is in the germination to four-leaf stage.

The action upon the growing plants is noted four weeks after treatment.

The summer wheat is not adversely effected but the accompanying weeds are destroyed or severely damaged as seen from Table VII in which the effects of the treatment are evaluated on an arbitrary scale ranging from 10 (no noticeable effect) to 0 (fully destroyed).

Table Vll Active Summer Slellaria C'henopo- Umca Galinsoga Agent, wheat media dium wens pamiflora kgJha. album Di-cyclohexyl-carbo-diimide 5 9 5 2 3 Dl-cyclohexyl-carbo-diimide 7 8 3 1 3 1 Untreated control 10 10 10 10 10 The results of the weed control treatment are tabulated V inTable VI. 40 EXAMPLE 7 Table VI The same composition as described in Example 6 is R1 R3 Active Corn Wheat Gazmso a suspended in water to a concentration of 2 kg. active Agent compound per 1,000 liters. C 1 C 1 1 o 0 Another composition containing 20 parts of N,N'-diyo ohexy yc ohexy 1 1 1 1.7 y v I CW1 o 0 ctylm CYOIOOCWL" 1 10 10 3 (cyclohexyl) carbodnmide dissolved in parts of xylene Isopropyl Phenyl 3 7 6 4.5 and 20 parts of tributylphenol-polyglcol-ether 1S emulsified in water in an analogous manner. Chenopodium Urlz'ca Lami m Both preparations are sprayed on carrot fields after geralbum 5 mination in such amounts as to deposit 2 kg./ha. of the C 1 1 0 5 active agent. gzfigg g 55 323 31: The emulsified preparation in this example shows even Isopro 1-- Phenyl 1 better eflfects on the weeds than the suspenslon.

Table VIII Active Galinsoga Thlaspz' Stellarla Cheno- N,N-Dl-cyclohexyl- Agent, Carrots parviflom arveme media podium earbodiimide kgJha. album Emulsificd 2 10 0' V o a 2 Suspended 2 10 3 1 6 5 0=fully destroyed. 10=n0 noticeable efiect.

EXAMPLE 6 EXAMPLE 8 A composition of 20 pts. or N,N'-di-(cyolohexy-l)-carbodiimide, 40 pts. of calcium carbonate and 40 pts. of the calcium'salt of lignin sul-fonic acid, prepared as men-- l tioned above, is dispersed in water to a concentration of 5 and 7'kg. active compound per 1,000 liters.

A mixture of N,N'-di-cyclohexyl-carbodiimide and isopropyl-N- (3-ch lorophenyl) -carbamuateis emulsified in water to aconcentration of 2 kg. c-arbodiimideand 1 kg. carbamate-compou-nd per 1,000 liters. The emulsion is sprayed on a carrot field, after germination, which is in- The suspensions are sprayed on summer wheat fields in' tested with br'oadleaved weeds and Boa annua.

After three weeks the carrots are not adversely affected while the broadleaved Weeds and Boa annua. are nearly fully destroyed.

Table IX 10 area not affected by the disease is a measure of the protective effect of the pest control agent. Three parallel tests are run for each concentration of each compound. Averages are tabulated in Table XI.

fungicidal effects of the pest control agents is determined after 7 to 8 days by measuring the surface area percentage 5 It is apparent from the table that many of the com pounds virtually completely suppress growth. of the fungus Active Br when applied in a concentration of 280 parts per mil {g g Carrots f z gg lion (ppm), and that the others have a strong effect on the fungus so as to reduce its growth by at least one half. The most active agents reduce fungus growth by Tfld 10 grb ljl gtll i f 83 percent when employed 1n amounts of as little as ii il i 2+1 10 0-1 0-1 17.5 ppm. vfitil'aitntli P133131: 10 10 10 Table X1 0 f n destroyei Percent effect against =no noticeable efieet. R Peronospomi P-P- EXAMPLE 9 280 70 17.5

A mixture of N,N'di-(cyclol1exyl)-carbodiimide and (yelopentyl gyelopentyl isopropyl-N-phenyl-carbamate is emulsified in Water to a g gggg lj I g g gfigg ffi concentration of 0.84 kg. carbodiimideand 1.68 kg. oarba- 1\ /I tl y1 do mate-compound per 1,000 liters. The emulsion is sprayed 55 on a sugar beet field and the action is noted 2 weeks after B treatment. 1.221513%? yl The mixture has no noticeable efifeot on the sugar beet tert-Butyl y yp ny leaves but the accompanying Weeds are severely damaged.

Table X Active Sugar Stellaria Galinsoga CIzenopz Agent, beets media parm'flora dzum album kg./ha.

N,N-di-(eyclohexyl) carbodiimide 0.84

8-9 0-1 0-1 0-1 Isopropyl-N-phenyl-earbamate- 1,68 Untreated control 10 10 10 10 10=r1o noticeable efieot. 0=fully destroyed.

The earbodiimide compounds of the invention also have desirable nematocidal and fungicidal effects as will be- EXAMPLE 11 come a arent from the tollowin exam les: pp p The nematodicidal efilects of carbodnmides of the inven- EXAMPLE 10 tion are tested on. larvae of The fungicidal effects ofthe carbodiimide compounds (A) Aphelenchoides ritzemabosi (Schwartz) ea n ss gig lg 0 ac e g n S n p (M) Meloidogyne incognito (Kofoid & White), chitwood The tests are performed in the laboratory under closely The larvae are freshly collected from plant parts and controlled uniform conditions. Grape leaves are placed are added to 2 ml of aqueous suspensions or emulsions in Petri dishes and are sprayed with uniform amounts of the active agentsat several concentrations. The liquid of aqueous emulsions ofthe active agents. The sprayed specimens are held at 20 C. for 24 hours. The permaterial is permitted to dry, and the leaves are then incentage of larvae still active is determined. Those not fected with suspensions of sporangia of the fungus. The showing any movement are considered killed. The percentage of larvae killed is given in Table XII. The test animals are identified by the initials as indicated above.

of the leaves showing evidence of Peronospora. The

Table XII Nematode larvae killed, percent Test at concentration of active agent R1 R2 Animal Cyelopentyl Cyclopentyl (A) 100 100 '100 100 (D) 100 I100 98 (M) 100 100 100 100 Oye1ohexy1 Cyclohexyl .....L (A) 100 100 100 100 (D) 100 100 98 98 I (M) 100 100 100 100 Oyc1oheptyl. Cycloheptyl (A) 100 98 98 95 (D) 100 100 98 95 (M) 100 V 100 100 100 Isopropyl Cyelooctyl (A) r 100 100 100 (D) 98 95 50 (M) 100 100 100 100 Allyl Cyclooctyl (A) 100 100 100 (D) 100 100 100 Table XlI-Cont1nued Nematode larvae killed, percent Test at concentration of active agent Rx Ra Animal Isopropyl Phenyl i (A) 100 100 100 95 (D) 100 98 0 (M) 100 100 100 100 tert.-Butyl d0 (A) 100 100 100 98 V (D) 100 100 80 70 (M) 100 100 100 100 HexyL --d0 (A) 100 100 100 100 (D) 100 100 98 80 (M) 100 100 100 100 Isopropyl 4-Ethoxyphenyl (A) 100 100 100 100 (D) 100 80 80 80 (M) 100 100 100 100 Do 4-Bromo-pheny1 (A) 100 100 100 100 (D) 100 100 100 98 (M) 100 100 100 100 Benzyl Phenyl (A) 100 100 100 100 (D) 98 80 50 50 (M) 100 100 100 100 Phenyl 4-Ohloro-Z-methyl-phenyl- (A) 100 100 70 50 (D) 30 0 0 0 (M) 100 100 S0 50 Isopropyl Benzyl.. (A) 100 100 100 100 I (D) 100 100 100 95 (M) 100 100 100 100 He'xyl Isopropyl (A) 100 100 100 95 (D) 100 100 50 30 (M) 100 r 100 100 100 tert.-Bntyl Furfuryl (A) 100 100 90 80 (D) 100 100 70 50 (M) 100 100 100 100 It h d b understood, of course, that the foregoing 30 applying to said fungi a fungicidal amount of a compound disclosure relates to only preferred embodiments of the plant protection method of the invention, and that numerous modifications and alterations may be'made therein without departing from the spirit and scope of the invention as set forth in the appended claims.

We claim:

1. A method of combatting weeds which comprises applying to said weeds a herbicidal amount of a compound having the formula wherein R and R are each selected from the group con- 7 sisting of (a) lower alkyl;

(b) cycloalkyl having a saturated carbon ring of five to eight members, one of said members being directly connected to one of the nitrogen atoms of said formula;

(0) lower alkenyl;

(d) radicals of the formula Alk-X, wherein All; is

lower alkylene and X is a member of the group consisting of lower alkoxy, phenyl, lauroxy, and morpholyl;

(e) radicals of the formula wherein n is an integer between four and seven. 7 3. A method as set'forth in claim 1, wherein said compound is N,N'-dicyclohexyl-carbodiimide.

4. A method of combatting fungi which comprises having the formula wherein R and R are each selected from the group consisting of (a) lower alkyl; (b) cycloalkyl having a saturated carbon ring of five to eight members, one of said members being directly connected to one of the nitrogen atoms of said formula; (0) lower alkenyl; i (d) radicals of the formula -AlkX, wherein Alk is lower alkylene and X is a member of the group consisting of lower alkoxy, phenyl, lauroxy, and morpholyl; (e) radicals of the formula wherein Y and Z are members of the group consisting of hydrogen, lowerialkyl, halogen, N0 lower alkoxy, and a (CH) chain jointly constituted by said Y and Z and attached to adjacent carbon atoms of the benzene ring of the last mentioned formula; (f) alkenoyl having substantially eighteen carbon atoms; and (g) furfuryl. V 5. A method as set forth in claim 4, wherein at least one of said R and R radicals is cycloalkyl.

6. A method as set forth in claim 4, wherein said com pound is N,N'-dicycloheXyl-carbodiimide.

7. A method of combatting nematodes which comprises applying to said nematodes a nematocidal amount of a compound of the formula connected to one of the nitrogen atoms in said i formula;

13 CA (c) lower alkenyl; (f) alkanoyl having substantially eighteen carbon (d) radicals of the formula -Alk--X, wherein Alk is atoms; and

lower alkylene and X is a member of the group con- (g) furfuryl. sisting of lower alkoxy, phenyl, lauroxy and morpholyl; 5 References Cited by the Examiner radicals of t e formula UNITED STATES PATENTS Y 2,942,025 6/ 6O Coles 260-551 Q OTHER REFERENCES Z 10 King: Insecticides and Repellants, US. Dept. Agri,

wherein Y and Z are members of the group i t- Agricultural Handbook No. 69, issued May 1954, p. 109. ing of hydrogen, lower alkyl, halogen, NO lower alkoxy, and a --(CH) chain jointly constituted JULIAN S. LEVITT, Primary Examiner.

by Said Y and Z and attached to adjacent Carbon M A Examiners atoms of the benzene ring of the last mentioned 15 formula; 

1. A METHOD OF COMBATTING WEEDS WHICH COMPRISES APPLYING TO SAID WEEDS A HERBICIDAL AMOUNT OF A COMPOUND HAVING THE FORMULA
 4. A METHOD OF COMBATTING FUNGI WHICH COMPRISES APPLYING TO SAID FUNGI A FUNGICIDAL AMOUNT OF A COMPOUND HAVING THE FORMULA 